Exhaust process for the dyeing of synthetic fiber materials

ABSTRACT

Exhaust process for the dyeing of synthetic fiber materials from organic water-immiscible solvents wherein are used as dyestuffs sulphonamide group containing disperse dyestuffs. There are obtained without originating waste waters dyeings with excellent fastness to washing, rubbing, light and sublimation.

This is a division of application Ser. No. 416,867 filed Nov. 19, 1973 which is a continuation of Ser. No. 161,282, filed July 9, 1971, now abandoned.

The invention relates to an exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents; more particlarly it concerns an exhaust process for the dyeing of synthetic fibre materials from organic water-immiscible solvents wherein are used as dyestuffs disperse dyestuffs containing sulphonamide groups.

Organic water-immiscible solvents suitable for the process according to the invention are those the boiling point of which lies betweem 40 and 170°C, e.g. aromatic hydrocarbons such as toluene, xylene; and halogenated hydrocarbons, especially aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1,1,1-trichloropropane, 1-chlorobutane, 2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane or dichlorohexane; as well as aliphatic fluorinated and fluoro-chlorinated hydrocarbons, such as perfluoro-n-hexane, 1,2,2-trifluoro-trichloroethane and trifluoro-pentachloropropane; aromatic chlorinated and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene, 1,1,1-trichloroethane and 1,1,1-trichloropropane have proved particularly satisfactory. Mixtures of said solvents can also be used.

The sulphonamide group-containing disperse dyestuffs to be used according to the invention may be based on any type of dyestuffs, provided these contain at least one sulphonamide group. The dyestuffs to be used according to the invention may belong, for example, to the series of metal-containing or metal-free mono- or polyazo dyestuffs or (azo)methine dyestuffs; to the series of anthraquinone dyestuffs and of condensation products thereof containing more than three fused rings; other suitable dyestuffs are oxazine, nitrodiphenylamine, naphthalic acid, di- and triphenyl-methane dyestuffs; naphtholactam condensation dyestuffs, quinophthalone dyestuffs, and dyestuffs based on naphthoquinone and naphthoquinonimine; as well as other condensation dyestuffs. In addition to the sulphonamide groups required by definition, the dyestuffs may contain other conventional substituents, such as halogen, alkyl, cycloalkyl, aralkyl, aryl, alkoxy, aryloxy, nitro, sulphone, optionally substituted carboxamide groups, optionally substituted or acylated amino groups, alkylthio and arylthio, hydroxy, hydroxyalkyloxy, aminoalkyloxy, cyano, cyanoalkyl, and differently substituted alkyl, aryl, aralkyl radicals, and the like.

The dyestuffs contain one or more sulphonamide groups which are linked to the aromatic nuclei of the basic ring system of the dyestuff itself or to aryl, aralkyl, or aliphatic groupings in external positions. The numer of sulphonamide groups preferably amounts to 1 to 3.

The sulphonamide groups are characterized by the formula ##EQU1## in which the radicals B and B₁, independently of one another, denote hydrogen or optionally substituted lower alkyl or alkenyl groups, aryl radicals or heteroaryl radicals. Furthermore, the radicals B and B₁ together may form a ring which may be interrupted by hetero atoms.

Examples of radicals B and B₁ are the methyl, ethyl or trifluoromethyl radicals; the β-hydroxy, β-chloro, β-bromo, β-methoxy, β-methylthio, β-methylsulphonyl or β-cyanoethyl groups; or an ethylene or β-chloro- or β-bromoethylene radical. If B or B₁ stands for an aryl radical, this is preferably a phenyl radical which may be substituted by one or more halogen atoms such as fluorine, chlorine or bromine; nitro groups; trifluoromethyl, hydroxy or lower alkoxy radicals; carboxyl or carboxamide groups; acylamino groups; sulphonamide or lower alkylsulphonyl radicals. Suitable heteroaryl radicals are, for example, the pyridyl, pyrrolyl, pyrimidinyl, furanyl, thienyl or sulpholanyl radicals. Examples of rings which may be formed by B and B₁ and may be interrupted by hetero atoms are the pyrrolidinyl, piperidinyl, morpholinyl, thiomorpholinyl or thiomorpholinyl dioxide rings.

Dyestuffs containing sulphonamide groups are known in large numbers and are prepared by conventional methods in that suitable dyestuff intermediates containing one or more sulphonamide groups linked to the nucleus or in an external position are converted into the desired final products while retaining the sulphonamide groups and, if desired, further conversion reactions are carried out in the latter. Obviously, it is also possible to start from dyestuffs containing one or more sulphonic acid groups and to convert the sulphonic acid groups into the corresponding amides in the usual way via reactive intermediate stages, such as e.g. the ester and acid chloride. In the case of azo dyestuffs, the usual conversion reactions are diazotisation and coupling; for most other dyestuffs classes they are condensation reactions.

Examples of suitable azo dyestuffs containing sulphonamide groups are the following compounds in which the radical ##EQU2## may have the following meaning: ##SPC1##

R₁ = h, c₂ h₅, ch₂ ch₂ oh, c₆ h₅, c₆ h₄ cl, C₆ H₄ COOH, CH₂.CH₂.CN, CH₂.CH₂.COOH, ##EQU3## R₂ = CH₃, COOH, ##EQU4## COO alkyl, Oalkyl R₃, R₄, R₅ = H, CH₃, C₂ H₅, OCH₃, OC₂ H₅ OCH₂ COOH, COOH, COOR, OCH₂ COOR, NO₂, Cl, Br, CN (R = alkyl), ##EQU5## (n = 1 - 4) R₆ = OH, NH₂ ##SPC2##

R₁, r₂, r₃ = h, ch₃, c₂ h₅, och₃, oc₂ h₅, cl, Br, OCH₂ COOR, NO₂, COOH, OCH₂ COOH, COOR (R = alkyl), NH-acyl, ##EQU6## (n = 1 - 4) R₄ = H, alkyl ##SPC3##

R₁, r₂ = h, ch₃, c₂ h₅, och₃, oc₂ h₅, cl, Br, NO₂

R₃ = alkyl, cycloalkyl

R₄ = h, cooh, ##EQU7## ##SPC4## r₁ = alkyl, aryl, ##EQU8## R₂ = H, COOH, ##EQU9## R₃ = alkyl, cycloalkyl ##SPC5##

R₁ = h, no₂, cl ##SPC6##

R₁, r₂ = h, ch₃, cl, Br, NO₂, OCH₃, CN

R₃ = h, ch₃, och₃, oc₂ h₅, oc₆ h₅ .

r₄, r₅ = h, ch₃, c₂ h₅, ch₂ ch₂ oh, ch₂.ch₂.cn, ch₂ ch₂ or₇ (r₇ = alkyl or acyl radical)

R₆ = h, nh.acyl, ##EQU10## (n = 0 -4) ##SPC7##

R₁, r₂, r₃ = h, ch₃, c₂ h₅, och₃, oc₂ h₅, och₂ cooh, cooh, och₂ coor, coor, no₂, cl, Br, CN, ##EQU11## R₄, R₅ = CH₃, C₂ H₅, CH₂ CH₂ OH, CH₂.CH₂.CN, CH₂ CH₂ OR₆ (R₆ = alkyl or acyl radical)

n = 0, 1, 2, 3. ##SPC8##

R₁, r₂ = h, ch₃, c₂ h₅, och₃, oc₂ h₅, no₂, cl, Br,

R₄, r₅ = ch₃ c₂ h₅, ch₂ ch₂ oh. ##SPC9##

r₁, r₂ = h, ch₃, cl, Br, NO₂, OCH₃,

R₃, r₄ = h, ch₃, och₃, oc₂ h₅, nh.acyl

R₅, r₆ = h, ch₃, c₂ h₅, ch₂ ch₂ oh, ch₂ ch₂ or₇ (r₇ = acyl radical),

R₇ = --so₂ -alkyl, --SO₂ -aryl, ##EQU12## (n = 0 - 4) ##SPC10##

R₁, r₂, r₃ = h, ch₃, c₂ h₅, och₃, oc₂ h₅, cl, Br, NO₂, COOH, ##EQU13## ##SPC11## R, R₂ = H, OH, OCH₃, Cl, NO₂, CH₃

R₃,r₄ = h, ch₃, och₃, c₂ h₅, oc₂ h₅ ##SPC12##

r₁, r₂ = h, oh, och₃, cl, NO₂, CH₃,

R₃, r₄ = h, ch₃, c₂ h₅, och₃, oc₂ h₅,

r₅ = h, ch₃, och₃, cooh, ##EQU14## ##SPC13## r₁, r₂, r₃ = h, ch₃, c₂ h₅, cl, Br, OCH₂ COOH, OCH₂ COOR, ##EQU15## R₄, R₅ = H, CH₃, C₂ H₅, OCH₃, OC₂ H₅,

n = 0, 1, 2, 3, 4. ##SPC14##

R₁, r₂, r₃, r₄, r₅ = h, ch₃, c₂ h₅, och₃. ##SPC15##

r₁, r₂, r₃, r₄ = h, ch₃, c₂ h₅, och₃, cl, NO₂, ##EQU16## R₅ = CH₃, COOH, COOalkyl, Oalkyl ##SPC16##

R₁, r₂ = h, cl, NO₂ ##SPC17##

R₁, r₂, r₃, r₄ = h, ch₃, c₂ h₅, och₃ ##SPC18##

r₁ = h, c₁ -c₄ -alkyl, C₁ -C₄ -alkoxy, aryloxy

R₂ = h, hal, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, -NH-acyl

R₃, r₄ = h, ch₃, c₂ h₅, ch₂.ch₂.oh, ch₂.oh₂.ch .o.acyl, CH₂.OH₂.ON ##SPC19##

R₁ = h, c₁ -c₄ -alkyl, C₁ -C₄ -alkoxy, arloxy

R₂ = h, hal, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, --NH-acyl

R₃, r₄ = h, ch₃, c₂ h₅, ch₂.ch₂.oh, .ch₂.ch₂.o.acyl, .CH₂.CH₂.ON ##SPC20##

X = h, ch₃, n--C₃ H₇, N--C₄ H₉

R₁ = ch₃, c₂ h₅, sec. C₄ H₉, CH₂ CH₂ OH, CH₂ CH₂ OOOOH₃, CH₂ CH₂ CN,

R₂ = h, c₁ -c₄ -alkyl, C₁ -C₄ -alkoxy,

R₃ = h, hal, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, --NH--CO--R' (R' = C₁ -C₆ -alkyl)

n = 0 - 4 ##SPC21##

R = ch₃, c₂ h₅, c₄ h₉.

suitable anthraquinone dyestuffs are, for example, those in which one or more sulphonamide groups stand in the anthraquinone molecule itself or in aryl or alkyl radicals which are linked to the anthraquinone molecule via bridge members such as amino, ether, thioether, sulphonamide or sulphonylamino groups.

The anthraquinone compounds may have the following constitutions, for example, the group ##EQU17## having the same meaning as above: ##SPC22##

one X = OH,

the other X = NO₂, NH₂, ##EQU18## furthermore, acylation products of amino-anthraquinones, e.g. of the formulae: ##SPC23##

with sulpho-carboxylic acids of the general formula ##EQU19##

X = alkylene, arylene, a bivalent heterocyclic radical, or with a compound of the formula ##SPC24##

and furthermore, the anthraquinone dyestuffs assembled in the following Table: ##SPC25##

The anthraquinone dyestuffs of the formula ##SPC26##

in which

R₁ means an amino group

R₂ means a hydroxy or amino group

X means --O-- or --S--

Y means a phenylene group and

D means ##SPC27##

have proved to be of special interest and among them the dyestuffs ##SPC28##

have proved to be especially valuable.

Among anthraquinone condensation products which contain sulphonamide groups and contain more than three fused rings, the following may be mentioned by way of example: Isothiazoloanthrones, such as ##SPC29## ##EQU20## Pyrazoloanthrones, such as ##SPC30## ##EQU21## furthermore, dyestuffs of the type ##SPC31## ##EQU22## ##SPC32## R = H, NH₂ ##SPC33##

Anthraquinone dyestuffs of the formulae given above are prepared according to the synthesis principles known in anthraquinone chemistry. Condensation reactions with appropriate starting compounds are suitable in the first instance for this purpose. For example, amino group-containing anthraquinone compounds in which the amino groups stand either in an external position or, preferably, in a position linked to the nucleus, can be condensed with suitable sulphoaryl-acid halides or anhydrides, e.g. sulphophenyl- or naphthyl-carboxylic acid or -sulphonic acid chlorides or bromides to form the corresponding acid amides; or, for example, anthraquinone compounds with mobile halogen atoms can be reacted with sulphoaryl-amines such as sulphophenyl- or sulphonaphthyl-amines to form the corresponding sulphoarylamino-anthraquinone derivatives, and the free sulpho groups still present in the resultant dyestuffs can be converted into sulphonamide groups in known manner. Alternatively, for example, anthraquinone compounds containing amino groups can be condensed with sulphonamido-aryl-acid halides or anhydrides, or e.g. anthraquinone compounds containing mobile halogen atoms can be condensed with sulphonamido-arylamines.

Anthraquinone ether and thioether derivatives in which sulphonamide groups are contained in alkyl, aralkyl or aryl radicals of the ether or thioether component, can be prepared according to similar synthesis principles. Another possibility of synthetising sulphonamide group-containing anthraquinone dyestuffs to be used according to the invention consists in that anthraquinone-acid halides, such as carboxylic acid and sulphonic acid chlorides or bromides, are converted into the corresponding amides or esters with the aid of suitable amino or hydroxy compounds which contain at least one additional sulphonamide group. Obviously, it is also possible to use for the present process also those anthraquinone compounds in which one or more sulphonamide groups stand in a position linked to the nucleus or in which sulphonamide groups linked to the nucleus as well as externally linked sulphonamide groups are present.

As representatives of nitro dyestuffs containing sulphonamide groups, there may be mentioned for example dyestuffs of the formula ##SPC34##

X = --so₂ -- or --CO--

Y = --nh-- or --O--

Z₁ and/or Z₂ = ##EQU23## R₁, R₂ = H, Cl, Br, F, CH₃, C₂ H₅, CH₃ O, OH, CN, NO₂,

R₃, r₄ = cf₃, cooh, o--ch₂ --cooh, --o--ch₂ --ch₂ --cooh, --cooalkyl, --NH-acyl, ##EQU24## or dyestuffs of the formula ##SPC35##

in which

R₁ means hydrogen, a halogen atom, a trifluoro, cyano, hydroxy, C₁ -C₄ -alkyl or -alkoxy, a hydroxymethyl or -ethyl, a hydroxy-ethylene-oxy, acylamino, alkylsulphonyl-amino, alkylsulphone, carboxamido, aminosulphonyl-alkyleneamino or sulphonamide group;

R₂ means hydrogen or a C₁ -C₄ -alkoxy group;

R₃ means hydrogen, a halogen atom, a hydroxy, hydroxy-ethyleneoxy, carboxamido, aminosulphonyl-alkyleneoxy or sulphonamide group;

X stands for the group --SO₂ -- or --CO; and

Y stands for --NH-- or --O--;

with the proviso that one of the radicals R₁, R₃ or ##SPC36##

is a sulphonamide group or a radical containing a sulphonamide group.

The nitro dyestuff of the formula ##SPC37##

has proved to be especially valuable.

In many cases it has proved advantageous for the dyebaths to contain small amounts of water, i.e. up to 1 percent by weight, preferably 0.5 percent by weight, referred to the weight of the organic solvent.

Furthermore, it has proved expedient in some cases to add non-ionic auxiliaries to the dyebaths. Suitable nonionic auxiliaries are primarily the known interface-active ethoxylation and propoxylation products of fatty alcohols, alkylphenols, fatty acid amides and fatty acids as well as mixtures thereof; the auxiliaries are used in an amount of 0.05 - 2 percent by weight, referred to the weight of the organic solvents. Instead of being immediately added to the dyebaths, the auxiliaries can also be used to advantage for pasting the sulphonamide group-containing dyestuffs and in this way be added to the dyebaths in the form of a dyestuff/auxiliary paste.

The synthetic fibre materials to be dyed according to the invention are primarily fibre materials of polyesters, such as polyethylene terephthalate, poly-cyclohexanedimethylene terephthalate, heterogeneous polyesters from terephthalic acid, sulphoisophthalic acid and ethylene glycol, or copolyether ester fibres from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol; cellulose triacetate, cellulose 21/2-acetate; polyacrylonitrile; synthetic polyamides such as hexamethylene-diamine adipate, poly-ε-caprolactam or 4-aminoundecanic acid; and polyurethanes. The fibre materials may be present in the most varied stages of processing, for example, as threads, loose material, combed material, yarn, as piece goods such as fabrics or knitted fabrics, or as ready-made goods.

Dyeing according to the invention is preferably carried out in closed apparatus, for example, by introducing the fibre materials at room temperature into the dyebath, heating the dyebath to 60° - 170°C and keeping it at this temperature until the bath is exhausted; this is usually the case after 10 - 60 minutes. After cooling to room temperature, the liquor is separated and the fibre materials are freed from any adhering solvent, optionally after a short rinsing with fresh organic solvent, by filtering with suction or by centrifuging and subsequent drying in a warm current of air. With the aid of the process according to the invention it is possible to dye synthetic fibre materials from organic solvents in a simple way, high dyestuff yields and excellent fastness properties being achieved.

The sulphonamide group-containing dyestuffs to be used according to the invention are largely insoluble in the organic water-immiscible solvents. They are distinguished from the dyestuffs hitherto used for dyeing synthetic fibre materials from organic solvents by their substantially better affinity and an increased fastness to sublimation.

It may be mentioned that mixtures of the dyestuffs to be used according to the invention sometimes give a better dyestuff yield than the individual dyestuffs.

The parts given in the following Examples are parts by weight.

EXAMPLE 1

100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from

1 part of the monoazo dyestuff 4-aminobenzene-sulphonic acid amide → 3-methyl-pyrazolone-(5) and

1000 parts tetrachloroethylene.

The bath is heated to 115°C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40°C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current. A strong yellow dyeing of excellent fastness to sublimation and very good fastness to washing and light is obtained.

An equally satisfactory yellow dyeing was obtained in the same way on a fabric of polycyclohexane-dimethylene terephthalate fibres.

Yellow dyeings of equally satisfactory fastness properties were also obtained when the dyestuff mentioned above was replaced with the same amount of one of the following monoazo dyestuffs:

    ______________________________________                                         Example                                                                               Dyestuff                  Shade                                         ______________________________________                                          2     3-nitro-4-amino-benzene-sulphonic acid                                                                   yellow                                               amide → 3-methyl-pyrazolone-(5)                                   3     2-amino-benzene-sulphonic acid amide                                                                     yellow                                               → 3-methyl-pyrazolone-(5)                                         4     2,5-dimethoxy-aniline → 3-methyl-                                                                 yellow                                               5-pyrazolone-1-sulphonic acid amide                                      5     2-nitro-aniline → 3-methyl-5-pyrazolone-                                                          yellow                                               1-sulphonic acid methylamide                                             6     4-methoxy-3-amino-benzene-sulphonic acid                                                                 yellow                                               n-butylamide → 1-phenyl-3-methyl-                                       5-pyrazolone                                                             7     3-nitro-4-amino-benzene-sulphonic acid                                                                   orange                                               amide → 1-phenyl-3-methoxy-5-amino-                                     pyrazole                                                                 8     2-nitro-4-chloro-aniline → 1-(3-morpho-                                                           orange                                               lino-sulphonyl-phenyl)-3-ethoxy-5-amino-                                       pyrazole                                                                 9     4-amino-benzene-sulphonic acid amide                                                                     yellow                                               → 1-phenyl-5-pyrazolone-3-carboxylic                                    acid ethyl ester                                                        10     4-amino-benzene-sulphonic acid amide                                                                     yellow                                               → 1-(3-carboxyphenyl)-3-methyl-5-                                       pyrazolone                                                              11     4-amino-benzene-sulphonic acid ethylamide                                                                yellow                                               → 1-phenyl-5-pyrazolone-3-carboxylic                                    acid                                                                    12     4-amino-benzene-sulphonic acid dimethyl-                                                                 yellow                                               amide → 1-phenyl-5-pyrazolone-3-                                        carboxylic acid amide                                                   13     3-nitro-4-amino-benzene-sulphonic acid                                                                   yellow                                               amide → 1-phenyl-5-pyrazolone-3-                                        carboxylic acid ethyl ester                                             14     2-methoxy-4-nitro-aniline → 1-(3-amino-                                                           yellow                                               sulphonyl-phenyl)-3-methyl-5-pyrazolone                                 15     4-amino-benzene-sulphonic acid-(di-2-                                                                    yellow                                               hydroxyethyl)-amide → 1-(2-cyanoethyl)-                                 3-methyl-5-pyrazolone                                                   16     4-amino-benzene-sulphonic acid ethylamide                                                                yellow                                               → 1-(2-carboxyethyl)-3-methyl-5-                                        pyrazolone                                                              17     2-cyano-4-nitro-aniline → 1-(3-amino-                                                             yellow                                               sulphonyl-phenyl)-3-methyl-5-pyrazolone                                 18     4-methyl-aniline → 1-(3-phenylamino-                                                              yellow                                               sulphonyl-phenyl)-3-methyl-5-pyrazolone                                 19     4-amino-benzene-sulphonic acid-dimethyl-                                                                 yellow                                               amide → 1-(3-aminosulphonyl-phenyl)-3-                                  methyl-5-pyrazolone                                                     20     3-nitro-4-amino-benzene-sulphonic acid                                                                   yellow                                               dimethylamide → 1-(3-chlorophenyl)-5-                                   pyrazolone-3-carboxylic acid                                            21     2-methoxy-5-nitro-aniline → 1-(2-amino-                                                           yellow                                               sulphonyl-ethyl)-3-methyl-5-pyrazolone                                  22     2-bromo-4-nitro-aniline → 1-hydroxy-                                                              yellow                                               benzene-2-sulphonic acid-(di-2-cyanoethyl)-                                    amide                                                                   23     4-ethoxy-aniline → 1-hydroxy-3-methyl-                                                            yellow                                               benzene-2-sulphonic acid-(4-chlorophenyl)-                                     amide                                                                   24     4-(4-pyrrolidinosulphonylbutoxy)-aniline                                                                 yellow                                               → 1-hydroxy-benzene-2-sulphonic acid                                    (2-pyridino)-amide                                                      25     3-amino-benzoic acid → 1-hydroxy-                                                                 yellow                                               benzene-2-sulphonic acid-(3-sulpholanyl)-                                      amide                                                                   26     4-amino-benzene-sulphonic acid amide                                                                     yellow                                               → 1-hydroxy-4-methyl-benzene                                     27     2-amino-benzene-sulphonic acid amide                                                                     yellow                                               → 1-hydroxy-4-cyclohexyl-benzene                                 29     3-nitro-4-amino-benzene-sulphonic acid amide                                                             yellow                                               → 1-hydroxy-4-methyl-benzene                                     29     3-nitro-5-chloro-4-amino-benzene-                                                                        yellow                                               sulphonic acid → 1-hydroxy-4-methyl-benzene                      30     4-amino-benzene-sulphonic acid-piperidide                                                                yellow                                               → 1-hydroxy-4-methyl-benzene-2-                                         carboxylic acid                                                         31     4-amino-benzene-sulphonic acid-(2-methyl-                                                                yellow                                               sulphonylethyl)-amide → 1-hydroxy-4-                                    methyl-benzene-2-sulphonic acid amide                                   32     4-methylsulphonylamino-aniline → 1-                                                               yellow                                               hydroxy-4-n-propyl-benzene                                              33     4-phenylsulphonylamino-aniline → 1-                                                               yellow                                               hydroxy-4-methyl-benzene                                                34     4-dimethylamino-sulphonylamino-aniline                                                                   yellow                                               → 1-hydroxy-4-ethyl-benzene                                      35     4-methylsulphonylamino-aniline                                                                           yellow                                               → 1-hydroxy-4-methyl-benzene-2-                                         carboxylic acid amide                                                   ______________________________________                                    

EXAMPLE 36

100 Parts of a fabric of triacetate fibres are introduced at room temperature into a dyebath prepared from

1 part of the monoazo dyestuff 4-methyl-sulphonylamino-aniline → 1-hydroxy-4-methyl-benzene and

1000 parts tetrachloroethylene.

The bath is heated to 110°C within 20 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. The liquor is then separated and the fabric is rinsed with fresh tetrachloroethylene at 40°C. After separation of the rinsing liquor, the dyed materials is freed from the adhering solvent by centrifuging and drying in an air current. A full brilliant yellow dyeing of excellent fastness properties is obtained.

EXAMPLE 37

100 Parts of yarn of acetate threads are introduced at about 22°C into a dyebath prepared from

1 part of the monoazo dyestuff 4-piperidyl-sulphonylamino-aniline → 1-hydroxy-4-methylbenzene,

1000 parts tetrachloroethylene

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether and

6 parts of water.

The bath is heated to 78°C within 20 minutes and kept at the same temperature for 45 minutes. After separation of the dye liquor and rinsing with fresh tetrachloroethylene, the dyed material is freed from the adhering solvent by filtering with suction and drying in an air current. A brilliant yellow dyeing is obtained.

EXAMPLE 38

100 Parts of yarn of polyacrylonitrile fibres are dyed in a dyebath prepared as described in Example 36. The bath is heated to 100°C within 20 minutes and kept at the same temperature for 30 minutes. After the usual washing and drying, there is obtained a yellow dyeing of good fastness properties.

EXAMPLE 39

100 Parts of a fabric of polyethylene terephthalate fibres are heated in a dyebath containing

1 part of the monoazo dyestuff 3-nitro-4-aminobenzene-sulphonic acid amide → 1-methyl-2,4-dihydroxy-quinoline in

1000 parts tetrachloroethylene

to 115°C within 10 minutes and dyed at the same temperature for 30 minutes. After separation of the liquor, rinsing and drying, there is obtained a brilliant greenish yellow dyeing of very good fastness to sublimation, washing and light.

When the above dyestuff was replaced with the same amount of one of the dyestuffs listed in the following Table, dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

    __________________________________________________________________________     Example                                                                             Dyestuff                Shade                                             __________________________________________________________________________     40   4-amino-benzene-sulphonic acid amide                                                                   yellow                                                 → 1-methyl-2,4-dihydroxy-quinoline                                 41   4-trifluoromethyl-2-amino-benzene-                                                                     yellow                                                 sulphonic acid amide → 1-methyl-2,4-                                    dihydroxy-quinoline                                                       42   4-chloro-3-amino-benzene-sulphonic acid                                                                yellow                                                 (2-hydroxyethyl)amide → 1-methyl-2,4-                                   dihydroxy-quinoline                                                       43   4-amino-benzene-sulphonic acid-(di-2-                                                                  yellow                                                 hydroxyethyl)-amide → 1-methyl-2,4-                                     dihydroxy-quinoline                                                       44   3-amino-benzene-sulphonic acid-(2-methyl-                                                              yellow                                                 thioethyl)-amide → 1-methyl-2,4-                                        dihydroxy-quinoline                                                       45   4-amino-benzene-sulphonic acid-(1-naphthyl)-                                                           yellow                                                 amide → 1-methyl-2,4-dihydroxy-quinoline                           46   3,5-dichloro-4-amino-benzene-sulphonic acid                                                            yellow                                                 dimethyl-amide → N-(2-cyanoethyl)-N-                                    ethyl-aniline                                                             47   3,6-dichloro-4-amino-benzene-sulphonic acid                                                            orange                                                 dimethyl-amide → N-(2-cyanoethyl)-N-                                    ethyl-aniline                                                             48   3-nitro-4-amino-benzene-sulphonic acid amide                                                           reddish                                                → N,N-(di-2-acetoxyethyl)-aniline                                                               yellow                                            49   3-nitro-5-bromo-4-amino-benzene-sulphonic                                                              yellowish                                              acid amide → N,N-(di-2-acetoxyethyl)-                                                           red                                                    aniline                                                                   50   3-nitro-4-amino-benzene-sulphonic acid                                                                 reddish                                                amide → 3-methyl-N,N-(di-2-acetoxy-                                                             yellow                                                 ethyl)-aniline                                                            51   3-cyano-5-nitro-4-amino-benzene-sulphonic                                                              yellowish                                              acid methylamine → N-ethyl-N-(2-acetoxy-                                                        red                                                    ethyl)-aniline                                                            52   3,5-dicyano-4-amino-benzene-sulphonic acid                                                             red                                                    amide → N,N-dimethyl-aniline                                       53   3-chloro-5-nitro-2-amino-benzene-sulphonic                                                             red                                                    acid amide → N,N-(di-2-propionyloxy-                                    ethyl)-aniline                                                            54   3-chloro-5-nitro-2-amino-benzene-sulphonic                                                             red                                                    acid → N,N-(di-2-methoxycarbonyl-                                       ethyl)-aniline                                                            55   3-cyano-5-nitro-2-amino-benzene-sulphonic                                                              bluish                                                 acid amide → 3-methyl-N,N-(di-2-                                                                red                                                    methoxycarbonyloxy-ethyl)-aniline                                         56   3,5-dichloro-4-amino-benzene-sulphonic acid                                                            orange                                                 methylamide → N-(2-pyrrolidylcarbonyl-                                  ethyl)-aniline                                                            57   3-cyano-5-bromo-4-amino-benzene-sulphonic                                                              reddish                                                acid diethylamide → N-[2-(3-methyl-                                                             orange                                                 phenylamino)-ethyl]-succinimide                                           58   5-methyoxy-2-amino-benzene-sulphonic acid                                                              yellowish                                              amide → N-(2-cyanoethyl)-N-(2-hydroxy-                                                          red                                                    ethyl)-aniline                                                            59   3-bromo-5-nitro-4-amino-benzene-sulphonic                                                              violet                                                 acid amide → 3-acetylamino-N,N-dimethyl                                 aniline                                                                   60   3-bromo-5-cyano-4-amino-benzene-sulphonic                                                              red-                                                   acid amide → 3-acetylamino-N,N-diethyl-                                                         violet                                                 aniline                                                                   61   3,5-dicyano-4-amino-benzene-sulphonic acid                                                             violet                                                 amide → 3-acetylamino-N,N-dimethylaniline                          62   3-bromo-5-nitro-4-amino-benzene-sulphonic                                                              violet                                                 acid amide → 2-methoxy-5-acetylamino-                                   N,N-dimethyl-aniline                                                      63   3-chloro-5-nitro-2-amino-benzene-sulphonic                                                             violet                                                 acid amide → 2-phenoxy-5-acetylamino-                                   N,N-dimethyl-aniline                                                      64   2-bromo-4,6-dinitro-aniline → 3-methyl-                                                         violet                                                 sulphonylamino-N,N-dimethylaniline                                        65   2-bromo-4-nitro-6-cyano-aniline                                                                        blue-                                                  → 3-chloromethylsulphonylamino-                                                                 violet                                                 N-(2-cyanoethyl)-aniline                                                  66   2,6-dicyano-4-nitro-aniline →                                                                   blue                                                   3-methylsulphonylamino-N,N-dimethyl-                                           aniline                                                                   67   2-bromo-4,6-dinitro-aniline → 3-phenyl-                                                         violet                                                 sulphonylamino-N,N-dimethyl-aniline                                       68   2-chloro-4,6-dinitro-aniline →                                                                  violet                                                 3-methylsulphonylamino-N-(2-hydroxy-                                           ethyl)-N-(2-cyanoethyl)-aniline                                           69   2-bromo-4,6-dinitro-aniline → 2-methoxy-                                                        blue                                                   5-methysulphonylamino-N,N-(di-2-                                               acetoxyethyl)-aniline                                                     70   2,6-dichloro-aniline → 3-dimethyl-                                                              reddish                                                sulphonyl-amino-N,N-(di-2-acetoxy-                                                                     yellow                                                 ethyl)-aniline                                                            71   3-bromo-5-nitro-4-amino-benzene-                                                                       brown                                                  sulphonic acid amide → 3-methylamino-                                   sulphonylmethylamino-N,N-dimethyl-                                             aniline                                                                   72   2-chloro-4-nitro-6-cyano-aniline →                                                              brown                                                  3-(3-ethylaminosulphonylpropylamino)-                                          N,N-diethyl-aniline                                                       73   2,6-dichloro-4-nitro-aniline →                                                                  yellow-                                                N-ethyl-N-(2-dimethylaminosulphonyl-                                                                   brown                                                  ethyl)-aniline                                                            74   4-dimethylsulphonylamino-aniline →                                                              reddish                                                3-methyl-N,N-(di-2-acetoxyethyl)-                                                                      yellow                                                 aniline                                                                   75   3-nitro-5-amino-benzene-sulphonic acid                                                                 orange                                                 (2-hydroxyethyl)-amide → N-(2-methoxy-                                  ethyl)-N-(2-methoxycarbonylethyl)-                                             aniline                                                                   76   2-bromo-4,6-dinitro-aniline → N-methyl-                                                         yellow                                                 sulphonyl-aniline                                                         77   2,5-dichloro-aniline → 3-methyl-N-                                                              reddish                                                ethyl-N-(2-methylsulphonylamino-                                                                       yellow                                                 ethyl)-aniline                                                            78   4-amino-benzene-sulphonic acid methyl-                                                                 yellow                                                 amide → N-phenylaniline                                            79   4-amino-benzene-sulphonic acid-thio-                                                                   yellow                                                 morpholid-S-dioxide                                                       80   4-(3-methylaminosulphonyl-benzoyl-                                                                     yellow                                                 amino)-aniline → 4-methyl-phenol                                   81   6-methylaminosulphonyl-2-amino-1,3-                                                                    red                                                    benzothiazole → N-(2-cyanoethyl)-N-                                     (2-acetoxyethyl-)aniline                                                  82   6-aminosulphonyl-2-amino-1,3-benzo-                                                                    red                                                    thiazole → N,N-(di-2-cyanoethyl)-                                       aniline                                                                   83   3-chloro-4-amino-benzene-sulphonic acid                                                                orange                                                 amide → 3-acetylamino-N,N-diethyl-                                      aniline                                                                   84   5-methylaminosulphonyl-2-amino-                                                                        bluish                                                 1,3-thiazole → N-ethyl-N-(2-carboxy-                                                            red                                                    ethyl)-aniline                                                            85   5-aminosulphonyl-2-amino-1,3-                                                                          red-                                                   thiazole → 3-acetylamino-N,N-dimethyl-                                                          violet                                                 aniline                                                                   86   4-(4-aminosulphonylphenyl)-2-amino-                                                                    yellowish                                              1,3,5-thiadiazole → N,N-(di-2-acetoxy-                                                          red                                                    ethyl)-aniline                                                            87   4-(4-methylaminosulphonylphenyl)-2-                                                                    red                                                    amino-1,3,5-thiadiazole → 3-acetyl-                                     amino-N,N-dimethyl-aniline                                                88   4-methylsulphonylamino-aniline →                                                                orange                                                 3-methyl-N,N(di-2-acetoxyethyl)-                                               aniline                                                                   89   4-phenylsulphonylamino-2-chloro-aniline →                                                       reddish                                                3-acetylamino-aniline   orange                                            90   2-chloro-4-nitro-aniline → 2-amino-                                                             red                                                    naphthalene-6-sulphonic acid methylamide                                  91   2-chloro-4-nitro-aniline → 2-amino-                                                             red                                                    naphthalene-6-sulphonic acid amide                                        92   4-methylsulphonylamino-2-nitro-aniline                                                                 red                                                    → 2-hydroxynaphthalene                                             93   4-methylsulphonylamino-aniline →                                                                red                                                    2-aminonaphthalene-5-sulphonic acid                                            methylamide                                                               94   4-amino-benzene-sulphonic acid amide →                                                          yellow                                                 1,2-dimethyl-indole                                                       95   4-aminoazobenzene → 2-hydroxy-                                                                  red                                                    naphthalene-6-sulphonic acid-N-methyl-                                         N-(2-hydroxyethyl)-amide                                                  96   4-aminoazobenzene → 2-hydroxy-                                                                  red                                                    naphthalene-6-sulphonic acid-N-methyl-                                         N-(2-acetoxyethyl)-amide                                                  97   4-amino-azobenzene-4'-sulphonic acid amide                                                             red                                                    → 2-hydroxynaphthalene                                             98   3-chloro-5-amino-benzene-sulphonic acid                                                                reddish                                                amide → N,N-(di-acetoxyethyl)-aniline                                                           yellow                                            99   4-methyl-5-aminosulphonyl-2-amino-1,3-                                                                 red                                                    thiazole → 3-acetylamino-N,N-dimethyl-                                  aniline                                                                   100  5-nitro-3-amino-benzoisothiazole-(2,1)                                                                 navy                                                   → 3-methylsulphonylamino-N,N-dimethyl-                                  aniline                                                                   101  5-nitro-3-amino-benzoisothiazole-(2,1)-                                                                red                                                    6-sulphonic acid amide → 3-acetylamino-                                 N,N-dimethyl-aniline                                                      __________________________________________________________________________

EXAMPLE 102

100 Parts of a knitted fabric of polyethylene terephthalate fibres are dyed in a dyebath containing

1 part of the disazo dyestuff 4-aminobenzene-sulphonic acid amide → aniline → phenol in

1000 parts tetrachloroethylene

at 115°C for 30 minutes. After the usual rinsing and drying, there is obtained a reddish yellow dyeing of very good fastness to sublimation, washing and light.

Dyeings of equally valuable fastness properties were also obtained when the above dyestuff was replaced with the same amount of one of the following disazo dyestuffs:

    ______________________________________                                         Example                                                                               Dyestuff                  Shade                                         ______________________________________                                         103    4-amino-benzene-sulphonic acid methyl-                                                                   reddish                                              amide → 2,5-dimethoxy-aniline → phenol                                                     orange                                        104    3-chloro-4-amino-benzene-sulphonic acid                                                                  orange                                               (4-chlorophenyl)-amide → 2-chloro-                                      aniline → phenol                                                 105    3-amino-toluene → 3-ethoxy-aniline →                                                       orange                                               1-hydroxy-benzene-2-sulphonic acid-(2-                                         hydroxyethyl)-amide                                                     106    4-chloro-3-amino-benzene-sulphonic acid                                                                  reddish                                              amide → 3-amino-toluene → salicylic                                                        yellow                                               acid                                                                    107    3-nitro-4-amino-benzene-sulphonic acid                                                                   reddish                                              amide → 3-amino-ethylbenzene → phenol                                                      yellow                                        108    2-amino-benzene-sulphonic acid amide →                                                            reddish                                              aniline → salicylic acid amide                                                                    yellow                                        109    4-amino-toluene → 3-amino-benzene-                                                                yellow                                               sulphonic acid amide → phenol                                    110    2,5-dichloro-aniline → aniline → 3-                                                        orange-                                              hydroxy-N-(4-aminosulphonylbutyl)-aniline                                                                brown                                         111    4-methylsulphonylamino-aniline → 3-amino-                                                         reddish                                              toluene → phenol   yellow                                        112    4-(3-methylaminosulphonylpropylamino)-                                                                   reddish                                              aniline → 3-methoxy-aniline → phenol                                                       yellow                                        113    4-(4-methoxyphenylsulphonylamino)-                                                                       reddish                                              aniline → 3-amino-ethylbenzene → phenol                                                    yellow                                        114    4-amino-benzene-sulphonic acid amide                                                                     orange                                               1-aminonaphthalene → phenol                                      115    3-nitro-4-amino-benzene-sulphonic acid                                                                   orange                                               amide → 2-amino-naphthalene → phenol                      116    aniline → 1-amino-naphthalene → 1-                                                         orange                                               hydroxy-benzene-2-sulphonic acid amide                                  117    3-amino-benzene-sulphonic acid (2-cyano-                                                                 reddish                                              ethyl)-amide →  aniline                                                                           yellow                                        118    4-amino-benzene-sulphonic acid amide →                                                            reddish                                              2-chloro-aniline → 4-tert.butyl-phenol                                                            yellow                                        119    4-amino-benzene-sulphonic acid amide                                                                     reddish                                              aniline → 4-hydroxy-toluene                                                                       yellow                                        120    4-amino-benzene-sulphonic acid amide →                                                            reddish                                              3-amino-toluene → 4-hydroxy-toluene                                                               yellow                                        121    aniline → 1-amino-naphthalene-8-                                                                  orange                                               sulphonic acid amide → phenol                                    ______________________________________                                    

EXAMPLE 122

50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from

1 part 1-amino-4-hydroxy-2-(4-aminosulphonylphenyl-thio-anthraquinone

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated to 120°C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor, the dyed material is rinsed with fresh solvent at 40°C and, after removal of the rinsing liquor, dried in an air current. A brilliant violet dyeing of excellent fastness to light and sublimation is obtained.

Equally satisfactory violet dyeings are obtained when the 500 parts tetrachloroethylene are replaced with the same amount of 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1,2-dichloropropane, 2-chlorobutane, 1,4-dichlorobutane, perfluoro-n-hexane, 1,2,2-trifluoro-trichloroethane, trifluoro-pentachloropropane, chlorobenzene, fluorobenzene, chlorotoluene or benzotrifluoride.

The dyestuff used in Example 122 had been prepared as follows: 15 parts 1-amino-4-hydroxy-2-phenylthioanthraquinone are dissolved in 76 parts chlorosulphonic acid, and 22.5 parts thionyl chloride are added at 20° - 25°C within 1 hour. The melt is stirred at 20° - 25°C for 3 hours, turned out on to ice, the precipitate is filtered off with suction and washed with ice-water until neutral. The product is subsequently introduced into 250 parts of 25% ammonia and stirred at 20° - 25°C for 5 hours. It is filtered off with suction, washed with water, and after drying there are obtained 18.5 parts 1-amino-4-hydroxy-2-(4-aminosulphonylphenylthio)-anthraquinone = 96% of theory.

EXAMPLE 123

100 Parts of fibre yarn of poly-ε-caprolactam are introduced at room temperature into a dyebath containing

1 part of the dyestuff mentioned in Example 122 in

1000 parts tetrachloroethylene.

The bath is heated to 100°C within 20 minutes and kept at the same temperature for 40 minutes while the liquor is vividly circulating. After this period of time, the liquor is separated, the dyeing is briefly rinsed with fresh solvent and dried in an air current after centrifuging. A brilliant violet dyeing of good fastness properties is obtained.

An equally satisfactory dyeing was also obtained on yarns of polyhexamethylene-diamine adipate fibres.

The strength of colour of the dyeing can be increased by ˜ 10% by the addition of

1 part oleic acid ethanolamide

1 part oleyl alcohol eicosaethylene glycol ether and

4 parts of water

to the dyebath.

EXAMPLE 124

100 Parts polyethylene terephthalate fabric are dyed at 115°C for 30 minutes in a dyebath consisting of

1 part 1-amino-4-hydroxy-2-(4-methylamino-sulphonylphenoxy)-anthraquinone,

3 parts oleic acid ethanolamide

3 parts oleyl alcohol eicosaethylene glycol ether

12 parts of water and

1600 parts tetrachloroethylene.

After rinsing with fresh tetrachloroethylene and drying, there is obtained a strong and brilliant red dyeing of very good fastness to sublimation, washing and light.

When the above dyestuff was replaced with the same amount of one of the dyestuff listed in the following Table, then dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

    ______________________________________                                         Example                                                                               Dyestuff                  Shade                                         ______________________________________                                         125    1-amino-4-hydroxy-2-[4-(2-methoxyethyl-                                                                  red                                                  amino)-sulphonyl-phenoxy]-anthraquinone                                 126    1-amino-4-hydroxy-2-[4-(2-hydroxyethyl-                                                                  red                                                  amino)-sulphonyl-phenoxy]-anthraquinone                                 127    1-amino-4-hydroxy-6-chloro-2-(4-amino-                                                                   red                                                  sulphonyl-phenoxy)-anthraquinone                                        128    1-amino-4-hydroxy-6,7-difluoro-2-                                                                        red                                                  (4-thiomorpholino-sulphonyl-phenoxy)-                                          anthraquinone                                                           129    1-amino-4-hydroxy-2-(4-methysulphonyl-                                                                   red                                                  aminophenoxy)-anthraquinone                                             130    1-amino-4-hydroxy-2-[2-(4-aminosulphonyl-                                                                red                                                  phenoxy)-ethoxy]-anthraquinone                                          131    1-amino-4-hydroxy-2-[2-(4-methylamino-                                                                   red                                                  sulphonylphenyl)-ethoxy]-anthraquinone                                  132    1-amino-4-hydroxy-2-[4-aminosulphonyl                                                                    red                                                  phenylthio)-ethoxy-]anthraquinone                                       133    1-amino-4-hydroxy-2-(4-diethylamino-                                                                     red                                                  sulphonylamino-phenoxy)-anthraquinone                                   134    1-amino-4-hydroxy-2-[4-(3-methoxy-                                                                       violet                                               propylamino)-sulphonyl-phenyl-thio]-                                           anthraquinone                                                           135    1-amino-4-hydroxy-2-[4-(2-hydroxy-                                                                       violet                                               ethylamino)-sulphonyl-phenyl-thio]-                                            anthraquinone                                                           136    1-amino-4-hydroxy-2-[4-chloro-2-(di-2-                                                                   violet                                               hydroxyethyl)-amino-sulphonyl-phenyl-                                          thio]-anthraquinone                                                     137    1-amino-4-hydroxy-2-(4-methylthio-3-                                                                     violet                                               amino-sulphonyl-phenyl-thio)-anthra-                                           quinone                                                                 138    1-amino-4-hydroxy-7-chloro-2-[(2-methyl-                                                                 violet                                               sulphonylethyl)-amino-sulphonyl-phenyl-                                        thio]-anthraquinone                                                     139    1-amino-4-hydroxy-2-(3-aminosulphonyl-                                                                   bluish                                               propylthio)-anthraquinone red                                           140    1-amino-4-hydroxy-2-(4-methylamino-                                                                      bluish                                               sulphonyl-benzylthio)-anthraquinone                                                                      red                                           141    1-amino-4-hydroxy-2-[2-(4-hexamethylene-                                                                 bluish                                               imino-sulphonyl-phenyl)-ethylthio]-                                                                      red                                                  anthraquinone                                                           142    1-amino-4-hydroxy-2-[2-(3-methyl-4-                                                                      bluish                                               aminosulphonyl-phenoxy)-ethyl-thio]-                                                                     red                                                  anthraquinone                                                           143    1-amino-4-hydroxy-2-(2-dimethylamino-                                                                    bluish                                               sulphonylethylthio)-anthraquinone                                                                        red                                           144    1-amino-4-methoxy-2-(4-methylamino-                                                                      yellow-                                              sulphonyl-phenoxy)-anthraquinone                                                                         red                                           145    1-amino-4-methoxy-2-(4-N-methyl-N-                                                                       red                                                  phenylamino-sulphonyl-phenyl-thio)-                                            anthraquinone                                                           146    1-amino-2-(4-morpholinosulphonyl-                                                                        orange                                               phenoxy)-anthraquinone                                                  147    1-amino-2-(4-aminosulphonyl-phenyl-thio)-                                                                yellow-                                              anthraquinone             red                                           148    1,4-dihydroxy-2-[4-(2-cyanoethylamino)-                                                                  orange                                               sulphonyl-phenoxy]-anthraquinone                                        149    1,4-dihydroxy-2-(4-aminosulphonyl-phenoxy)-                                                              orange                                               anthraquinone                                                           150    1,4-dihydroxy-2-(4-methylamino-                                                                          scarlet                                              sulphonyl-phenyl-thio)-anthraquinone                                    151    1,4-diamino-2-[4-(3-cyano-phenyl-amino)-                                                                 blue-                                                sulphonyl-phenoxy]-anthraquinone                                                                         violet                                        152    1,4-diamino-2,3-bis-(4-amino-sulphonyl-                                                                  red-                                                 phenoxy)-anthraquinone    violet                                        153    1,4-diamino-2-(4-amino-sulphonyl-phenyl-                                                                 reddish                                              thio)-anthraquinone       blue                                          154    1,4-diamino-2-[4-(3-methoxypropylamino)-                                                                 reddish                                              sulphonyl-phenyl-sulphonyl]-anthraquinone                                                                blue                                          155    1,4-diamino-anthraquinone-2-sulphonic acid                                                               reddish                                              (4-ethyl-amino-sulphonyl-phenyl) ester                                                                   blue                                          158    1-hydroxy-4-(3-methylamino-sulphonyl-                                                                    blue-                                                phenyl-amino)-anthraquinone                                                                              violet                                        157    1-hydroxy-4-(4-methyl-3-amino-sulphonyl-                                                                 blue-                                                phenyl-amino)-anthraquinone                                                                              violet                                        158    1-hydroxy-4-(4-methylsulphonyl-amino-                                                                    reddish                                              phenyl-amino)-anthraquinone                                                                              blue                                          159    1-amino-4-[4-(2-cyanoethyl-2-hydroxy-                                                                    blue                                                 ethyl-amino-sulphonyl)-phenyl-amino]-                                          anthraquinone                                                           160    1-amino-4-(2,6-diethyl-4-methyl-3-                                                                       reddish                                              amino-sulphonyl-phenyl-amino)-anthra-                                                                    blue                                                 quinone                                                                 161    1-amino-2-bromo-4-(4-methoxy-3-amino-                                                                    reddish                                              sulphonyl-phenylamino)-anthraquinone                                                                     blue                                          162    1-amino-2-phenyl-thio-4-(4-methyl-3-                                                                     blue                                                 amino-sulphonyl-phenylamino)-anthra-                                           quinone                                                                 163    1-amino-2-phenyl-sulphonyl-4-(3-amino-                                                                   green-                                               sulphonyl-phenylamino)-anthraquinone                                                                     ish                                                                            blue                                          164    1-amino-4-(4-amino-sulphonyl-phenyl-                                                                     red                                                  thio)-anthraquinone                                                     165    1-amino-2-(4-amino-sulphonyl-phenoxy)-                                                                   pink                                                 4-(4-methylphenyl)-sulphonyl-amino)-                                           anthraquinone                                                           166    1-amino-2-(4-amino-sulphonyl-phenoxy)-                                                                   pink                                                 4-methyl-sulphonyl-amino-anthraquinone                                  167    1-amino-anthraquinone-2-sulphonic acid                                                                   red                                                  (4-methoxyphenyl-amide)                                                 168    1-amino-4-hydroxy-anthraquinone-2-                                                                       red                                                  sulphonic acid-(3-trifluoromethyl-phenyl-                                      amide)                                                                  169    1,4-diamino-anthraquinone-2-sulphonic acid                                                               blue                                                 amide                                                                   170    1,4-diamino-anthraquinone-2-sulphonic acid                                                               blue                                                 (2-methoxy-ethyl)-amide                                                 171    1,5-dihydroxy-4,8-diamino-anthraquinone-                                                                 blue                                                 2-sulphonic acid ethylamide                                             172    1,5-dihydroxy-4,8-diamino-anthraquinone-                                                                 blue                                                 2,6-disulphonic acid-(3-methoxypropyl)-                                        amide                                                                   173    1,4-diamino-2-[5-methylaminosulphonyl-                                                                   blue                                                 benzoxazolyl-(2)]-anthraquinone                                         174    1-amino-4-(4-methylphenyl-amino)-                                                                        blue                                                 anthraquinone-2-sulphonic acid-(2-hydroxy-                                     ethyl)-amide                                                            175    1-amino-4-cyclohexyl-amino-anthraquinone-                                                                blue                                                 2-sulphonic acid amide                                                  176    1-(3-aminosulphonyl-propyl-amino)-                                                                       red                                                  anthraquinone                                                           177    1,4-bis-(3-amino-sulphonyl-propyl-                                                                       blue                                                 amino)-anthraquinone                                                    178    1,5-dihydroxy-4,8-diamino-2-(4-hydroxy-                                                                  blue                                                 3-ethylamino-sulphonyl-phenyl)-                                                anthraquinone                                                           179    1,5-dihydroxy-4,8-diamino-3-(4-hydroxy-                                                                  blue                                                 3-methylamino-sulphonyl-phenyl)-anthra-                                        quinone                                                                 180    1,5-dihydroxy-8-nitro-4-(ethylamino-                                                                     blue                                                 sulphonyl-phenylamino)-anthraquinone                                    181    1,8-dihydroxy-5-nitro-4-(3-amino-                                                                        blue                                                 sulphonyl-phenylamino)-anthraquinone                                    182    1,5-dihydroxy-8-amino-4-(3-methylamino-                                                                  blue                                                 sulphonyl-phenylamino)-anthraquinone                                    183    1,8-dihydroxy-5-amino-4-(3-amino-                                                                        blue                                                 sulphonyl-phenylamino)-anthraquinone                                    184    1,5-dihydroxy-8-amino-x-chloro-4-                                                                        blue                                                 (3-amino-sulphonyl-phenylamino)-                                               anthraquinone                                                           185    1,5-dihydroxy-8-nitro-x-bromo-4-                                                                         blue                                                 (3-amino-sulphonyl-phenylamino)-                                               anthraquinone                                                           186    1,8-dihydroxy-5-amino-x-bromo-4-                                                                         blue                                                 (3-amino-sulphonyl-phenylamino)-                                               anthraquinone                                                           187    1,8-dihydroxy-5-amino-x-bromo-4-                                                                         blue                                                 (3-amino-sulphonyl-phenylamino)-                                               anthraquinone                                                           188    1,8-dihydroxy-5-methylamino-4-                                                                           blue                                                 (4-methyl-3-amino-sulphonyl-phenyl-                                            amino)-anthraquinone                                                    189    1,9-isothiazolanthrone-2-sulphonic acid                                                                  yellow                                               (4-bromo-phenyl)-amide                                                  190    5-(2-aminosulphonyl-ethylamino)-1,9-                                                                     yellow                                               isothiazoloanthrone                                                     191    1,9-pyrazoloanthrone-2-sulphonic acid-N-                                                                 yellow                                               (2-hydroxyethyl)-N-phenyl-amide                                         192    5-(2-amino-sulphonyl-ethylamino)-1,9-                                                                    yellow                                               pyrazoloanthrone                                                        193    4-(3-amino-sulphonyl-phenylamino)-                                                                       red                                                  N-methyl-1,9-anthrapyridone                                             194    7-(2-hydroxyethyl)-amino-sulphonyl-                                                                      red                                                  3,4-phthaloyl-acridone                                                  195    7-(3-methoxypropyl)-amino-sulphonyl-                                           2-amino-3,4-phthaloyl-acridone                                          196    1,8-naphthoylene-benzimidazole-Bz-3-                                                                     yellow                                               sulphonic acid methylamide                                              197    1,8-naphthoylene-benzimidazole-4-                                                                        yellow                                               sulphonic acid amide                                                    198    1,8-naphthoylene-benzimidazole-4,5-                                                                      yellow                                               dicarboxylic acid-(2-methoxy-ethylimide)-                                      Bz-3-sulphonic acid ethylamide                                          199    phthaloylene-(1,8-naphthopyrimidine)-                                                                    yellow                                               3- or 8-sulphonic acid amide                                            200    4-(3-amino-sulphonyl-phenyl-amino)-                                                                      yellow                                               1,9-isothiazolo-anthrone                                                201    5-(3-amino-sulphonyl-phenyl-amino)-                                                                      yellow                                               1,9-isothiazolo-anthrone                                                202    4-(3-methylamino-sulphonyl-phenyl-                                                                       yellow                                               amino)-1,9-pyrazolo-anthrone                                            203    5-[3-(2-methoxyethyl-amino-sulphonyl)-                                                                   yellow                                               phenyl-amino]-1,9-pyrazolo-anthrone                                     ______________________________________                                    

EXAMPLE 204

100 Parts polyethylene terephthalate filaments are dyed in a dyebath consisting of

1 part 4-phenylamino-3-nitrobenzene-sulphonic acid amide

3 parts oleic acid ethanolamide

3 parts oleyl alcohol eicosaethylene glycol ether

12 parts of water and

1600 parts tetrachloroethylene

at 115°C for 30 minutes while the liquor is vividly circulating, they are centrifuged and rinsed with tetrachloroethylene at 40°C for 5 minutes. A strong greenish yellow dyeing of very good fastness to sublimation, washing and light is obtained.

An equally satisfactory dyeing is obtained when the tetrachloroethylene is replaced with the same amount of 1,1,2-trichloroethane.

When 1 part 4-phenylamino-3-nitrobenzene-sulphonamide is replaced with a mixture of 0.5 parts 4-phenylamino-3-nitrobenzene-sulphonic acid amide and 0.5 parts 4-(4-methoxyphenylamino)-3-nitrobenzene-sulphonamide, then a somewhat more reddish strong dyeing is obtained.

Similar dyeings are also obtained when the polyethylene terephthalate filaments are replaced with fibres of anion-modified polyethylene terephthalate (Dacron 64) or anion-modified polyhexamethylene-diamine adipate (Nylon T 844).

The dyestuff used in Example 204 had been prepared as follows: 900 parts of n-butanol saturated with ammonia are mixed with 550 parts of 79% 4-chloro-3-nitrobenzene sulphochloride and the mixture is stirred at 55° - 60°C for 1 hour. 200 Parts aniline were added and the mixture was heated to boiling temperature while slowly introducing ammonia, until the dyestuff formation was completed. After cooling, the crystallised product was filtered off with suction, washed with methanol and water and after drying there were obtained 460 parts 4-phenylamino-3-nitrobenzene-sulphonic acid amide = 92% of theory; m.p. 155°C.

EXAMPLE 205

100 Parts of polycarbonate filaments are dyed in a dyebath consisting of

1 part 4-(4-methoxy-phenylamino)-3-nitrobenzenesulphonic acid amide

2.5 parts oleic acid ethanolamide

2.5 parts oleyl alcohol eicosaethylene glycol ether

10 parts of water and

1000 parts tetrachloroethylene

as described in Example 204. A yellow dyeing of very good fastness to sublimation, washing and light is obtained.

When the dyestuffs given in Examples 204 and 205 were replaced with the same amount of one of the dyestuffs listed in the following Table, then dyeings of equally satisfactory fastness properties were obtained in the shades stated in the Table:

    ______________________________________                                         Example                                                                               Dyestuff                 Shade                                          ______________________________________                                         206    4-(4-ethoxy-phenylamino)-3-nitro-                                                                       reddish                                               benzene-sulphonic acid methylamide                                                                      yellow                                         207    4-(2-methoxy-phenylamino)-3-nitro-                                                                      reddish                                               benzene-sulphonic acid dimethylamide                                                                    yellow                                         208    4-phenylamino-3-nitro-benzene-sulphonic                                                                 yellow                                                acid-(di-2-hydroxyethyl)-amide                                          209    4-(4-phenyl-phenylamino)-3-nitro-                                                                       yellow                                                benzene-sulphonic acid amide                                            210    4-(4-phenoxy-phenylamino)-3-nitro-                                                                      reddish                                               benzene-sulphonic acid   yellow                                         211    4-(4-azobenzeneamino)-3-nitro-benzene-                                                                  reddish                                               sulphonic acid-(di-2-hydroxyethyl-amide                                                                 yellow                                         212    4-[4-(2-hydroxyethoxy)-phenylamino]-                                                                    reddish                                               3-nitro-benzene-sulphonic acid phenyl-                                                                  yellow                                                amide                                                                   213    4-(4-benzyloxy-phenylamino)-3-nitro-                                                                    reddish                                               benzene-sulphonic acid morpholide                                                                       yellow                                         214    4-(3-methoxy-phenylamino)-3-nitro-                                                                      reddish                                               benzene-sulphonic acid-(4-aminosulphonyl-                                                               yellow                                                phenyl)-amide                                                           215    4-(4-methoxycarbonyl-phenylamino)-3-                                                                    greenish                                              nitro-benzene-sulphonic acid-(2-hydroxy-                                                                yellow                                                ethyl)-amide                                                            216    4-(2,4-dimethoxy-phenylamino)-3-nitro-                                                                  reddish                                               benzene-sulphonic acid amide                                                                            yellow                                         217    4-(4-carboxy-phenylamino)-3-nitro-                                                                      greenish                                              benzene-sulphonic acid ethylamide                                       218    4-[4-(2-hydroxyethyl-aminosulphonyl)-                                                                   greenish                                              phenylamino]-benzene-sulphonic acid-                                                                    yellow                                                (2-hydroxyethyl)-amide                                                  219    4-(3-fluoro-phenylamino)-3-nitro-                                                                       greenish                                              benzene-sulphonic acid-(2-methoxyethyl-                                                                 yellow                                                amide                                                                   220    4-(3-trifluoromethyl-phenylamino)-3-                                                                    greenish                                              nitro-benzene-sulphonic acid-(2-cyano-                                                                  yellow                                                ethyl)-amide                                                            221    4-(3,4-dichloro-phenylamino)-3-nitro-                                                                   greenish                                              benzene-sulphonic acid-(3-methoxypropyl)-                                                               yellow                                                amide                                                                   222    4-(3-cyano-phenylamino)-3-nitro-                                                                        yellow                                                benzene-sulphonic acid-(4-methylamino-                                         carbonyl-phenyl)-amide                                                  223    4-(2-nitro-phenylamino)-3-nitro-                                                                        greenish                                              benzene-sulphonic acid piperidide                                                                       yellow                                         224    4-(4-methyl-phenylamino)-3-nitro-                                                                       yellow                                                benzene-sulphonic acid amide                                            225    4-(4-ethyl-phenylamino)-3-nitro-                                                                        yellow                                                benzene-sulphonic acid-[4-(2-hydroxy-                                          ethoxy)-phenyl]-amide                                                   226    4-(4-aminosulphonyl-phenylamino)-3-                                                                     greenish                                              nitro-benzene-sulphonic acid-(di-2-hydroxy-                                                             yellow                                                ethyl)-amide                                                            227    4-(4-aminosulphonyl-phenylamino)-3-                                                                     greenish                                              nitro-benzene-sulphonic acid-(3-diethyl-                                                                yellow                                                amino-sulphonyl-phenyl)-amide                                           228    4-(4-acetylamino-phenylamino)-3-                                                                        yellow                                                nitro-benzene-sulphonic acid ethylamide                                 229    4-(4-methylsulphonylamino-phenylamino)-                                                                 yellow                                                3-nitro-benzene-sulphonic acid phenylamide                              230    4-(4-methylsulphonylamino-phenylamino)-                                                                 yellow                                                3-nitro-benzene-sulphonic acid-(2-hydroxy-                                     ethyl)-amide                                                            231    4-phenylamino-4-nitro-benzene-sulphonic                                                                 greenish                                              acid-(4-aminosulphonyl-phenyl)-amide                                                                    yellow                                         232    4-(4-methoxy-phenylamino)-3-nitro-                                                                      reddish                                               benzene-sulphonic acid-(3-methylamino-                                                                  yellow                                                sulphonyl-phenyl)-amide                                                 233    4-(4-ethoxy-phenylamino)-3-nitro-                                                                       reddish                                               benzene-sulphonic acid-[3-(2-cyanoethyl-                                                                yellow                                                aminosulphonyl)-phenyl]-amide                                           234    4-(4-methyl-phenylamino)-3-nitro-                                                                       yellow                                                benzene-sulphonic acid-(4-aminosulphonyl-                                      phenyl)-amide                                                           235    4-(3-trifluoromethyl-phenylamino)-3-                                                                    greenish                                              nitro-benzene-sulphonic acid-[3-(2-cyano-                                                               yellow                                                ethyl-2-hydroxyethyl-aminosulphonyl)-                                          phenyl]-amide                                                           236    4-phenylamino-3-nitro-benzene-sulphonic                                                                 greenish                                              acid-[4-(2-aminosulphonylethoxy)-phenyl]-                                                               yellow                                                amide                                                                   237    4-[4-(3-aminosulphonyl-propoxy)-                                                                        reddish                                               phenyl-amino]-3-nitro-benzene-sulphonic                                                                 yellow                                                acid-(3-chloro-phenyl)-amide                                            238    4-phenylamino-3-nitro-benzene-sulphonic                                                                 yellow                                                acid-(4-aminosulphonyl-phenyl) ester                                    239    4-(4-methoxy-phenylamino)-3-nitrobenzene-                                                               reddish                                               sulphonic acid-(3-methylamino-sulphonyl-                                                                yellow                                                phenyl) ester                                                           240    4-(3-ethoxy-phenylamino)-3-nitrobenzene- reddish                               sulphonic acid-[4-(di-2-hydroxy-ethyl-                                                                  yellow                                                sulphonylamino)-phenyl] ester                                           241    4-(4-aminocarbonyl-phenylamino)-3-                                                                      greenish                                              nitrobenzene-sulphonic acid-(4-ethylamino-                                                              yellow                                                sulphonyl-phenyl) ester                                                 242    4-(3-acetylamino-phenylamino)-3-nitro-                                                                  yellow                                                benzene-sulphonic acid-(4-aminosulphonyl-                                      phenyl) ester                                                           243    4-phenylamino-3-nitro-benzoic acid                                                                      yellow                                                (4-aminosulphonyl-phenyl) amide                                         244    4-(4-ethoxyphenylamino)-3-nitro-                                                                        reddish                                               benzoic acid-[3-(2-hydroxyethylamino-                                                                   yellow                                                sulphonyl)-phenyl]-amide                                                245    4-(2,4-dimethoxy-phenylamino)-3-nitro-                                                                  reddish                                               benzoic acid-(4-methylaminosulphonyl-                                                                   yellow                                                phenyl)-amide                                                           246    4-(4-methyl-phenylamino)-3-nitro-                                                                       yellow                                                benzoic acid-(3-methylaminosulphonyl-                                          phenyl)-amide                                                           247    4-(4-nitro-phenylamino)-3-nitro-                                                                        yellow                                                benzoic acid-(3-pyrrolidinosulphonyl-                                          phenyl)-amide                                                           248    4-(3-bromo-phenylamino)-3-nitro-                                                                        yellow                                                benzoic acid-(4-hydroxy-3-n-propyl-                                            amino-sulphonyl-phenyl)-amide                                           249    4-(4-acetylamino-phenylamino)-3-nitro-                                                                  yellow                                                benzoic acid-(4-thiomorpholinosulphonyl-                                       phenyl)-amide                                                           250    4-(4-methylsulphonylamino-phenylamino)-                                                                 yellow                                                3-nitro-benzoic acid-(3-dimethylamino-                                         sulphonyl-phenyl)-amide                                                 251    4-phenylamino-3-nitro-benzoic acid-(4-                                                                  yellow                                                aminosulphonyl-phenyl) ester                                            252    4-(4-methoxy-phenylamino)-3-nitro-                                                                      yellow                                                benzoic acid-(3-methylaminosulphonyl-                                          phenyl) ester                                                           253    4-(3-methysulphonylamino-phenylamino)-                                                                  yellow                                                3-nitro-benzoic acid-[4-(3-hydroxypropyl-                                      aminosulphonyl)-phenyl] ester                                           254    4-(4-methylsulphonyl-phenylamino)-3-                                                                    greenish                                              nitro-benzene sulphonic acid-4-(amino-                                                                  yellow                                                sulphonyl-phenyl)-amide                                                 255    4-(4-methylsulphonyl-phenylamino)-3-nitro-                                                              greenish                                              benzene sulphonic acid-(2-hydrozyethyl)-                                                                yellow                                                amide                                                                   256    4-(3-hydroxymethyl-phenylamino)-3-                                                                      yellow                                                nitro-benzene-sulphonic acid-(4-methyl-                                        amino-sulphonyl-phenyl)-amide                                           257    4-(3-hydroxymethyl-phenylamino)-3-                                                                      yellow                                                nitro-benzene-sulphonic acid-morpholide                                 258    4-(4-hydroxyethyl-phenylamino)-3-nitro-                                                                 yellow                                                benzene-sulphonic acid-(3-aminosulphonyl-                                      phenyl)-amide                                                           259    4-(4-hydroxyethyl-phenylamino)-3-nitro-                                                                 yellow                                                benzene-sulphonic acid amide                                            ______________________________________                                    

EXAMPLE 260

100 Parts of yarn of polyethylene terephthalate fibres are dyed in a dyebath consisting of

1 part of the quinophthalone dyestuff of the formula ##SPC38##

2.5 parts oleic acid ethanolamide

2.5 parts oleyl alcohol

10 parts of water and

1600 parts tetrachloroethylene

as described in Example 204. A clear yellow dyeing is obtained, which is characterised by good fastness to sublimation, washing and light.

An equally satisfactory dyeing is obtained when the above quinophthalone-sulphonamide dyestuff is replaced with a bromination product which contains about 1 bromine atom per molecule and can be obtained in known manner by bromination in nitrobenzene or glacial acetic acid.

Clear yellow dyeings are also obtained when the dyestuff mentioned in Example 260 is replaced with equal amounts of the quinophthalene-sulphonic acid amides listed in the following Table:

    ______________________________________                                                                        B                                                                              N∠                                        Example                                                                               R.sub.1     R.sub.2                                                                              R.sub.3                                                                              B.sub.1                                         ______________________________________                                         261    H           H     H     NH--CH.sub.3                                    262    H           H     H     N(CH.sub.3).sub.2                               263    H           H     H     NH--C.sub.2 H.sub.5                             264    H           H     H     NH--CH.sub.2 --CH.sub.2 --OH                    265    H           H     H     N(CH.sub.2 --CH.sub.2 --OH).sub.2               266    H           H     H     NH--CH.sub.2 --CH.sub.2 --CN                    267    Cl          H     H     NO                                              268    Br          H     H     NH.sub.2                                        269    Cl          Cl    H     NH--CH.sub.3                                    270    NO.sub.2    H     H     NH.sub.2                                        271    CH.sub.3 O  H     H     NH--CH.sub.2 --CH.sub.2 --OH                    272    CH.sub.3.CO.NH                                                                             H     H     N(CH.sub.3).sub.2                               273    H           H     CH.sub. 3                                                                            NH.sub.2                                        274    H           H     CH.sub.3 O                                                                           NH.sub.2                                        ______________________________________                                    

Greenish yellow dyeings are obtained when the quinophthalone-sulphonamide dyestuff mentioned in Example 260 is replaced with equal parts of one of the methine dyestuffs of the formulae ##SPC39##

or with a styryl dyestuff of the formula ##SPC40##

EXAMPLE 275

100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from

1 part 1-amino-4-hydroxy-2-[4-(4'-hydroxyanilinosulphonyl)-phenoxy]-anthraquinone and

1000 parts tetrachloroethylene.

The bath is heated to 115°C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40°C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current.

There is obtained a strong red dyeing of excellent fastness to washing, light, rubbing and sublimation.

An equivalent red dyeing was obtained in the same way on a knitted fabric of poly-ε-caprolactame.

EXAMPLE 276

50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from

1 part 1-amino-4-hydroxy-2-[4-(4'-hydroxyanilinosulphonyl)-phenoxy]-anthraquinone and

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated to 120°C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor, the dyed material is rinsed with fresh solvent at 40°C and, after removal of the rinsing liquor, dried in an air current. A brillant red dyeing of excellent fastness to washing, rubbing, light and sublimation is obtained.

EXAMPLE 277

100 parts of fibre yarn of poly-ε-caprolactame are introduced at room temperature into a dyebath containing

1 part 1,4-diamino-2-[4-(4'-hydroxyanilinosulphonyl)-phenylthio]-anthraquinone in

1000 parts tetrachloroethylene.

The bath is heated to 100°C within 20 minutes and kept at the same temperature for 40 minutes while the liquor is vividly circulating. After this period of time, the liquor is separated, the dyeing is briefly rinsed with fresh solvent and dried in an air current after centrifuging. A brillant reddish blue dyeing of excellent fastness to washing, light, rubbing and sublimation is obtained.

An equivalent dyeing was obtained in the same manner on a yarn of poly-hexamethylene diamine adipate fibres.

EXAMPLE 278

100 Parts of a fabric of textured polyethylene terephthalate fibres are introduced at room temperature, without previous cleaning, into a dyebath prepared from

1 part 4-(4-hydroxyphenylamino)-3-nitro-benzenesulphonic acid-4-(hydroxyphenyl)-amide and

1000 parts tetrachloroethylene.

The bath is heated to 115°C within 10 minutes and kept at the same temperature for 30 minutes, while the liquor is vividly circulating. The liquor is then separated and the dyed material is rinsed with fresh solvent at about 40°C for 5 minutes. After separating of the rinsing liquor, the dyed material is centrifuged and dried in an air current. A strong yellow dyeing of excellent fastness to washing, rubbing, light and sublimation is obtained.

An equivalent yellow dyeing was obtained in the same manner on a fabric of poly-ε-caprolactame fibres.

EXAMPLE 279

50 Parts of a fabric of polyester fibres are introduced at room temperature into a dyebath prepared from

1 part 4-(4-hydroxyphenylamino)-3-nitro-benzene-sulphonic acid-(4-hydroxyphenyl)-amide

1.5 parts oleic acid ethanolamide

1.5 parts oleyl alcohol eicosaethylene glycol ether

6 parts of water and

500 parts tetrachloroethylene.

The bath is heated at 120°C within 10 minutes and kept at the same temperature for 45 minutes while the liquor is vividly circulating. After separation of the dye liquor, the dyed material is rinsed with fresh solvent at 40°C and, after removal of the rinsing liquor, dried in an air current. A brillant yellow dyeing of excellent fastness washing, rubbing, light and sublimation is obtained. 

I claim:
 1. Process for dyeing synthetic fiber material by exhaustion comprising introducing synthetic fiber material into a dyebath which is a dispersion consisting essentially ofA. organic solvent; B. a monoazo or disazo dyestuff containing 1 to 3 sulfonamide groups and largely insoluble in said dyebath; and C. up to 1% by weight of said organic solvent of water; said organic solvent consisting of water immiscible aliphatic halogenated hydrocarbon; anddyeing at a temperature of 60° to 170°C for 10-60 minutes until the dyebath is exhausted; said monoazo or disazo dyestuff being free of reactive groups, acid groups and carboxamide groups.
 2. Dyeing process of claim 1 in which said monoazo or disazo dyestuff is a monazo dyestuff having the formula ##SPC41##in which R₁ stands for hydrogen, a sulphonamide group, a C₁ -C₄ alkyl radical which may be substituted by a cyano, carboxy or sulphonamide group, or for an aryl radical which may be substituted by chlorine or by a carboxy or sulphonamide group; R₂ means a C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -carbalkoxy, carboxy or carboxamide group; R₃ means a C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitro or sulphonamide group; R₄ means hydrogen, chlorine, a C₁ -C₄ -alkoxy, cyano, nitro or sulphonamide group; R₅ means a hydroxy or amino group,with the proviso that at least one of the radicals R₁, R₂ or R₃ is a sulphonamide group or a radical containing a sulphonamide group.
 3. Dyeing process of claim 1 in which said monoazo or disazo dyestuff is a monoazo dyestuff having the formula ##SPC42##in which R₁, r₂ and R₃, independently of one another, stand for hydrogen, halogen, a C₁ -C₄ -alkoxy, --O--C₁ -C₄ -alkylene-sulphonamide, carboxyl, nitro, acylamino, alkyl- or arylsulphonamido or sulphonamide group; R₄ means a C₁ -C₄ -alkyl, cycloalkyl or sulphonamide group; R₅ means hydrogen, a carboxy, carboxamide or C₁ -C₄ -alkyl group,with the proviso that at least one of the radicals R₁, R₂, R₃ or R₄ is a sulphonamide group or a radical containing a sulphonamide group.
 4. Dyeing process of claim 1 in which said dyestuff has the formula ##SPC43##in which R₁ means a sulphonamide group and R₂ means hydrogen, chlorine, a nitro or trifluoromethyl group.
 5. Dyeing process of claim 1 in which said dyestuff has the formula ##SPC44##in which R₁ means hydrogen and R₂ means a pyrrolidino-carbonyl-ethyl, succinimidoylethyl, 2-cyanoethyl or methylsulphonyl, phenyl or 2-nitrophenyl group, or R₁ and R₂, independently of one another, mean a C₁ -C₄ -alkyl group, a 2-hydroxy, 2-C₁ -C₄ -alkoxy, 2-cyano, 2-C₁ -C₄ -acyloxy, 2-carboxy, 2-C₁ -C₄ -alkoxycarbonyl, 2-alkoxy-carbonyloxy, 2-carboxamido, 2-aminosulphonylamino, C₁ -C₄ -alkylsulphonylamino-ethyl group or a benzyl group; R₃ stands for hydrogen, a C₁ -C₄ -alkoxy or aryloxy group; R₄ stands for hydrogen, a C₁ -C₄ -alkyl, C₁ -C₄ -acylamino, C₁ -C₄ -alkylsulphonylamino, arylsulphonylamino, aminosulphonylamino, aminosulphonyl-alkylene-amino or amino-sulphonyl-aminoalkylene-amino group; D means the radical of a carbocyclic diazo component which may be substituted by one or more halogen atoms, cyano, nitro, C₁ -C₄ -alkoxy, aminosulphonyl, aminosulphonylamino, C₁ -C₄ -alkylsulphonylamino, arylsulphonylamino or sulphonamide groups, or stands for the radical of a heterocyclic diazo component,with the proviso that at least one of the radicals R₁, R₂, R₄ or D is a sulphonamide group or a radical containing a sulphonamide group.
 6. Dyeing process of claim 1 in which said dyestuff has the formula ##SPC45##in which R₁ means a nitro, sulphonamide, C₁ -C₄ -alkylsulphonamino or arylazo group; R₂ means hydrogen or chlorine; R₃ means hydrogen or a sulphonamide group; and R₄ means a hydroxy or amino group,with the proviso that at least one of the radicals R₁ and R₃ is a sulphonamide group or a radical containing a sulphonamide group.
 7. Dyeing process of claim 1 in which said dyestuff has the formula ##SPC46##in which R₁ and R₂, independently of one another, stand for hydrogen, chlorine, a C₁ -C₄ -alkyl, nitro or sulphonamide group; R₃ and R₄, independently of one another, stand for hydrogen, chlorine, a C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or sulphonamide group, or for a grouping --CH=CH--CH=CH-- required for the formation of a naphthalene ring; R₅ stands for hydrogen, a C₁ -C₄ -alkyl, cycloalkyl, carboxyl, carboxamide, sulphonamide or aminosulphonylalkyleneamine group,with the proviso that at least one of the radicals R₁, R₂, R₃, R₄ and R₅ is a sulphonamide group or a radical containing a sulphonamide group.
 8. Dyeing process of claim 1 in which said dyestuff is the coupled product of diazotized 4-aminobenzenesulphonic acid and 3-methyl-pyrazolone(5).
 9. The process of claim 1 in which said synethetic fiber material is polyester, polyamide, cellulose, triacetate, cellulose 21/2 acetate, polyacrylonitrile, or polyurethane.
 10. The process of claim 1 in which said synthetic fiber material is polyester.
 11. The process of claim 1 in which said synthetic fiber material is polyamide.
 12. The process of claim 1 in which said dyebath contains 0.05 to 2% by weight of non-ionic dyeing auxiliary based on the weight of said aliphatic halogenated hydrocarbon. 